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EP4051722B1 - Polyolefin-based laminating adhesive composition and recyclable laminate - Google Patents

Polyolefin-based laminating adhesive composition and recyclable laminate Download PDF

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Publication number
EP4051722B1
EP4051722B1 EP20796971.8A EP20796971A EP4051722B1 EP 4051722 B1 EP4051722 B1 EP 4051722B1 EP 20796971 A EP20796971 A EP 20796971A EP 4051722 B1 EP4051722 B1 EP 4051722B1
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EP
European Patent Office
Prior art keywords
layer
polyolefin
film substrate
adhesive composition
laminate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP20796971.8A
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German (de)
English (en)
French (fr)
Other versions
EP4051722A1 (en
Inventor
Yinzhong Guo
Tuoqi LI
Sudhanwa Dewasthale
Jian Wang
Thorsten Schmidt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
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Dow Global Technologies LLC
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Publication date
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Publication of EP4051722A1 publication Critical patent/EP4051722A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • C08G18/6208—Hydrogenated polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6547—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for

Definitions

  • the present invention is related to a polyolefin-based laminating adhesive composition for producing a mechanical recyclable material, a process of producing the polyolefin-based laminating adhesive composition for producing a mechanical recyclable material, a mechanically recyclable multi-layer laminate, a mechanically recyclable packaging article, and a process for producing a mechanically recyclable multi-layer laminate.
  • the invention is set out in the appended set of claims,
  • Traditional flexible packaging design is based on laminating various functional layers composed of different materials such as polyethylene terephthalate (PET), bi-axially oriented polypropylene (BOPP), metalized PET or oriented polypropylene (OPP), aluminum foils, and Nylon/polyimide, with a sealable layer such as low density polyethylene (LDPE) and sealable OPP. Due to laminating together different materials, the generated flexible packaging material becomes non-recyclable because, hereto date, there is yet no economically practical and technically efficient process to separate the different film layers and to recycle each film material individually.
  • PET polyethylene terephthalate
  • BOPP bi-axially oriented polypropylene
  • OPP metalized PET or oriented polypropylene
  • LDPE low density polyethylene
  • Conventional lamination adhesives used heretofore have included either acrylic-based or polyurethane-based adhesives.
  • Using such conventional adhesives to laminate a combination of different polyolefin films e.g., the combination of HDPE and LEPE; BOPE and LDPE; BOPP and LDPE; and BOPP and BOPP
  • the adhesives are usually highly crosslinked, limiting the feasibility of making traditional packaging designs using such adhesives ready for recycle.
  • Multilayer co-extrusion is another widely adopted industrial process to fabricate lamination structures.
  • package recyclability it is a challenge to prepare packaging materials containing pre-oriented films such as BOPE and BOPP, because the high temperature stage associated with extrusion tends to cause shrinkage of these pre-oriented films.
  • functional films like metalized films or foil are employed in the co-extrusion fabrication process to form lamination structures, multilayer co-extrusion cannot, or barely, be used.
  • the invention provides a polyolefin-based laminating adhesive composition for producing a mechanical recyclable material, the adhesive composition comprising a mixture of:
  • the invention provides a process for producing the polyolefin-based laminating adhesive composition as described herein, comprising mixing: (a) at least one saturated polyolefin polyol; and (b) at least one aliphatic multi-functional isocyanate compound.
  • the present invention is directed to a mechanically recyclable multi-layer laminate comprising:
  • the invention provides a mechanically recyclable packaging article made from the laminate as described herein.
  • the invention provides a process for producing a mechanically recyclable multi-layer laminate comprising the steps of:
  • Polyolefin polyol herein means a hydroxyl terminated polyolefin including straight chain molecules, branched molecules, and mixtures thereof.
  • the polyolefin polyol can also be di-hydroxyl functional, multi-hydroxyl functional, or a mixture thereof.
  • Mechanism recyclability with reference to a used packaging material, herein means the capability of directly recycling a used package material made from a multilayer laminated film structure; wherein the recycling is carried out mechanically to re-film the recycled material without having to: (1) pre-separate the various film layers of the multi-layer laminated film; (2) pre-clean the residual adhesive present in the recycled material; and (3) add compatibilizers to the adhesive used to form the multilayer laminated film structure of the recycled material.
  • Temperatures are in degrees Celsius (°C), and "ambient temperature” means between 20 °C and 25 °C, unless specified otherwise.
  • the multi-layer laminate structure of the present invention includes the combination of at least two film layer substrates adhered together by an adhesive composition or formulation layer.
  • the multi-layer laminate product includes: (a) a first heat resistant film substrate of for example, HDPE, BOPP, or BOPE; (b) a second heat sealable film substrate of for example LDPE; and (c) a layer of the polyolefin-based laminating adhesive composition described herein below for binding the layers (a) and (b).
  • a first heat resistant film substrate of for example, HDPE, BOPP, or BOPE
  • a second heat sealable film substrate of for example LDPE for example, LDPE
  • a layer of the polyolefin-based laminating adhesive composition described herein below for binding the layers (a) and (b).
  • One or more other optional film substrates can be used to produce the above multi-layer laminate structure, if desired.
  • the first layer, component (a), of the present invention can include one or more layers of, for example, HDPE, MDPE, BOPP, BOPE and mixtures thereof.
  • the first layer can include, for example, HDPE, BOPP, and BOPE.
  • the thickness of the first film layer used to form the recyclable multi-layer laminate product of the present invention can be, for example, from 25 ⁇ m to 150 ⁇ m in one embodiment, from 30 ⁇ m to 100 ⁇ m in another embodiment and from 35 ⁇ m to 75 ⁇ m in still another embodiment.
  • the second film layer, component (b), of the present invention can include one or more layers of for example, LDPE, CPP, sealable OPP, and mixtures thereof.
  • the thickness of the second film layer used to form the recyclable multi-layer laminate product of the present invention can be, for example, from 20 ⁇ m to 100 ⁇ m in one embodiment, from 25 ⁇ m to 75 ⁇ m in another embodiment and from 30 ⁇ m to 60 ⁇ m in still another embodiment.
  • the present invention includes a polyolefin-based lamination adhesive composition for use in producing mechanically recyclable laminated packaging materials.
  • the layer of adhesive composition, component (c), used to bind the first and second film layers, components (a) and (b), respectively, includes at least one layer of a polyolefin-based laminating adhesive composition; wherein the polyolefin-based laminating adhesive composition for use in producing a mechanically recyclable material includes a mixture of: (i) at least one polyolefin polyol; and (ii) at least one aliphatic multi-functional isocyanate compound.
  • the adhesive composition includes a reactive mixture of: (i) at least one polyolefin polyol and (ii) at least one aliphatic multi-functional isocyanate compound.
  • Other optional components (iii) can be added to the adhesive composition if needed.
  • optional components can include dimer fatty diols, catalysts, and other additives such as wetting agents and adhesion promoters.
  • the polyolefin polyols, component (i), used for making the polyolefin-based laminating adhesive composition useful in the present invention include one or more polyolefin polyols.
  • the polyolefin polyol, component (i) of the above polyolefin-based laminating adhesive composition includes polyolefin polyols having the following general chemical Structure (I):
  • the polyolefin polyols of Structure (I) above has a functionality of ⁇ 2.
  • the polyolefin polyols of Structure (I) above have a molecular weight of from 500 to 7,000 in one general embodiment.
  • the polyolefin-based lamination adhesive of the present invention has several advantages compared to known lamination adhesives including, for example, the adhesive: (1) allows laminated packaging materials to be mechanically recyclable without conducting the step of films separation; (2) has a significantly low infrared (IR) absorbance (which is similar to the polyolefin material) compared to traditional polyurethane adhesives (e.g., polyester polyols, polyether polyols, and combinations thereof); (3) has good adhesion performance no matter dry bond strength or chemical resistance, which allows constructed recyclable packaging to be used for hot-fill medium performance applications; (4) can be applied by a solvent-free process or a solvent-based process with additional solvents; and (5) can avoid overprinting varnishes (OPV) to protect the inks on top of packaging by revise printing in BOPP/LDPE and BOPE/LDPE structures, which brings the clarity of printed information as direct print but needs OPV.
  • IR infrared
  • Polyolefin polyols having the above Structure (I) include, for example, hydroxyl-terminated saturated polybutadiene, hydroxyl-terminated polyethylene, hydroxyl-terminated polypropylene, hydroxyl-terminated saturated hydrocarbons and mixtures thereof. Two or more of the above polyolefin polyols can be used in a mixture, where the hydroxyl functional group is at least 2 and above.
  • the polyolefin polyols can include commercially available compounds having the above general chemical Structure (I) including, for example, saturated polybutadiene polyols with different molecular weights, such as KRASOL HLBH-P2000 and KRASOL HLBH-P 3000 (available from Total) and KRATON LIQUID L-2203 (available from Kraton); and mixtures thereof.
  • KRASOL HLBH-P2000 and KRASOL HLBH-P 3000 available from Total
  • KRATON LIQUID L-2203 available from Kraton
  • polyolefin polyol of Structure (I) above has a functionality of ⁇ 2; a functionality of from ⁇ 2 to 10 in another embodiment; and a functionality of from ⁇ 2 to 5 in still another embodiment.
  • polyolefin polyol of Structure (I) above has a molecular weight of from 500 to 7,000 in one general embodiment; from 1,000 to 5,000 in another embodiment; from 1,100 to 4,000 in still another embodiment; and from 1,500 to 3,000 in yet another embodiment.
  • the amount of polyolefin polyol used in making the polyolefin-based laminating adhesive composition of the present invention can be, for example, from 10 wt % to 95 wt % in one embodiment, from 40 wt % to 90 wt % in another embodiment and from 60 wt % to 80 wt % in still another embodiment, based on the total amount of compounds in the adhesive composition.
  • the aliphatic multi-functional isocyanate, component (b), used for making the polyolefin-based laminating adhesive composition of the present invention can include, for example, one or more aliphatic multi-functional isocyanate compounds.
  • the aliphatic multi-functional isocyanate can be, hexamethylene diisocyanate (HDI) dimer or trimer; 4,4'-methylenebis(cyclohexyl isocyanate (HMDI) dimer or trimer; isophorone diisocyanate (IPDI) dimer or trimer; or mixtures thereof.
  • aliphatic multifunctional isocyanates which have carbon atoms in the range of from 6 to 40 in one embodiment, from 6 to 22 in another embodiment, and from 6 to 18 in still another embodiment, can also be used in the present invention.
  • the aliphatic multi-functional isocyanate can include, for example, HDI trimer.
  • the aliphatic multi-functional isocyanate can include commercially available compounds such as MOR-FREE TM C-33 (available from The Dow Chemical Company).
  • the amount of aliphatic multi-functional isocyanate used in making the polyolefin-based laminating adhesive composition of the present invention can be, for example, from 5 wt % to 40 wt % in one embodiment, from 8 wt % to 30 wt % in another embodiment and from 10 wt % to 25 wt % in still another embodiment, based on the total amount of compounds in the adhesive composition.
  • the respective amounts of polyisocyanate and the polyol are typically chosen such that there is a small excess of isocyanate (NCO) groups.
  • the amount of components (a) and (b) are at a stoichiometry ratio (molar ratio) of isocyanate (NCO) groups to hydroxyl (OH) groups (NCO to OH) of from 1.7 to 1.0 of NCO to 1 OH, from 1.5 to 1.0 of NCO to 1 OH in another embodiment, from 1.4 to 1.0 of NCO to 1 OH in still another embodiment, and from 1.4 to 1.0 of NCO to 1 OH in yet another embodiment.
  • the polyols having the above general chemical Structure (I) can be optionally combined with other optional compounds.
  • the other optional compounds include, for example, but are not limited to, saturated fatty dimer diols or triols such as PRIPOL TM 2030 or DEV TM 1242, or mixture thereof.
  • the loading of the other optional compound in total formulation, in weight percent (wt %) can be for example from 0 wt % to 30 wt % in one embodiment, from 0 wt % to 20 wt % in another embodiment, and from 0 wt % to 10 wt % in still another embodiment.
  • the thickness of the adhesive layer used to bind the first and second layers together to form the recyclable multi-layer laminate product of the present invention can be, for example, from 0.5 ⁇ m to 5 ⁇ m in one embodiment, from 1 ⁇ m to 4 ⁇ m in another embodiment and from 1.5 ⁇ m to 3 ⁇ m in still another embodiment.
  • the multi-layer laminate structure of the present invention is produced by applying the adhesive composition described above onto at least a portion of the surface of a heat resistant film substrate to form an adhesive layer on the surface of the film substrate.
  • the application of the adhesive composition can be carried out by conventional means known in the art of applying adhesive compositions or formulation.
  • the adhesive composition can be applied using conventional equipment and processes such as a solventless hot roll laminator for solventless composition, a solvent-based Gravure roll laminator, and a solvent-based FLEXO laminator for solvent-containing compositions.
  • the process for producing a multi-layer laminate product includes, for example, the steps of:
  • Step (I) is carried out by treating the polyolefin films with corona treater, as is normally done in a conventional lamination process, with a power in the range of from 1 kwz power to 3 kwz power in one embodiment, and from 1.5 kwz power to 2.5 kwz power in another embodiment.
  • Step (II) of the process includes applying the adhesive composition to at least a portion of the surface of the first heat resistant film substrate and/or to at least a portion of the surface of the second film substrate to form an adhesive layer between the first and second film substrates.
  • the application of the adhesive composition can be carried out, for example, at a temperature of from 40 °C to 80 °C in one embodiment, from 50 °C to 70 °C in another embodiment, and from 60 °C to 65 °C in still another embodiment. If the temperature is below 40 °C, the viscosity of the adhesive composition is too high to process. If the temperature is > 80 °C, the adhesive composition has a short (e.g., ⁇ 1 hr) pot-life and shrinking of the polyolefin film can occur.
  • Step (III) of the above process is carried out by combining the first and second film substrates together with the adhesive layer under lamination, sufficient to form a multi-layer laminate structure after coating the adhesive on the first film and/or the second film and contacting the two films together.
  • the two films are laminated together to form a laminated structure at 60 °C with a typical nip roll pressure of from 15 m/min to 310 m/min in one embodiment, from 20 m/min to 150 m/min in another embodiment, and 30 m/min to 100 m/min in still another embodiment.
  • the multi-layer film structure from step (III) can be cured at room temperature for 14 days in one embodiment, at a temperature of 40 °C for 7 days in another embodiment, or at a temperature of 40 °C in ⁇ 4 days with a catalyst present in the adhesive layer.
  • the curing temperature of the laminate structure can be from 20 °C to 50 °C in one embodiment, from 25 °C to 45 °C in another embodiment, and from 30 °C to 45 °C in still another embodiment.
  • the laminate can be: (1) recycled; and (2) used in medium performance food packaging applications.
  • the recyclability property of the multi-layer laminate structure can be from 50 % to 100 % in one embodiment; from 70 % to 100 % in another embodiment, and from 90 % to 100 % in still another embodiment.
  • the "recyclability" property of the laminate structure of the present invention can be measured by the laminate's properties including, for example, the laminate's: (1) mechanical properties (e.g., tensile modulus), (2) thermal properties (e.g., differential scanning calorimetry [DCS]) and dynamic mechanical spectroscopy [DMS]), (3) rheology properties (e.g., complex viscosity), and (4) IR absorbance properties by comparing the same properties to that of a laminate structure of the prior art.
  • Other properties, such as clarity and gel content, of the films present in the multi-layer laminate structure of the recycled materials can be measured by microscopy, if desired, to further determine the recyclability of the laminate film structure.
  • a broad embodiment of a process of producing a polyolefin-based laminating adhesive composition for use in making a mechanically recyclable laminated multi-layer packaging product includes, for example, simply thoroughly mixing: (a) the polyolefin polyol described above; (b) the aliphatic multi-functional isocyanate described above; and (c) any optional ingredients to form an adhesive mixture which can be processed via conventional mixing equipment and techniques used for making mixtures.
  • the components (a)-(c) are mixed, for example, at a temperature of from 20 °C to 80 °C in one embodiment, from 30 °C to 75 °C in another embodiment, and from 50 °C to 70 °C in still another embodiment. Below a temperature of 20 °C, the viscosity of the composition will be too high and a high viscosity will result in a low mixing efficient of components (a)-(c); and a temperature above 80 °C is too high of a temperature which will result in the adhesive composition have a short pot life (e.g., ⁇ 1 hr).
  • a short pot life e.g., ⁇ 1 hr
  • the process can include the one or more optional step(s).
  • one optional step may include mixing the composition with an over-head batch mixer to form a batch material or mixing the composition in a nozzle continuously during pumping of the composition.
  • the resultant adhesive composition can be used to prepare a mechanically recyclable laminated multi-layer packaging article or product.
  • Some of the advantageous properties exhibited by the resulting laminating adhesive composition produced according to the above-described process can include, for example, the adhesive: (1) has a low IR absorbance; (2) has good adhesion performance to polyolefin films and good chemical resistance; (3) can be applied by a solvent-free or a solvent-based process; and (4) is used to form laminated films with a good appearance.
  • the mixing viscosity of the adhesive composition at 65 °C is ⁇ 5,000 mPa.s in one embodiment, ⁇ 3,500 mPa.s in another embodiment, and ⁇ 2,500 mPa.s in still another embodiment.
  • the viscosity of the adhesive composition at 65 °C can be from 1,500 mPa.s to 2,500 mPa.s. If the viscosity of the composition is above 5,000 mPa.s, the coating process using such composition becomes difficult to perform in a solventless process.
  • the adhesion performance property of the adhesive composition can be measured by measuring the T-peel bond strength of the composition.
  • the T-peel bond strength is measured on a 25 mm strip of laminate sample at a rate of 250 mm/min on an Instron tensile tester with a 200 N loading cell. Three strips are tested for each laminate sample and high and mean bond strengths are recorded together with the failure mode. In the case of film tear and film stretch, the high value is reported. In other failure modes, the average T-peel bond strength is reported.
  • Typical failure modes include: “AF” for adhesive failure (adhesive with primary), “AT” for adhesive transfer (adhesive with secondary), “AS” for adhesive split (cohesive failure of adhesive), “FT” for film tear (destruct bond), “FS” for film stretch (destruct bond), and “MT” for metal transfer.
  • the polyolefin polyol and aliphatic isocyanate curing system is used for producing a recyclable multi-layer laminate product as described above.
  • the polyolefin polyol and aliphatic isocyanate curing system can also be used for surface over printing, varnish for the recyclable packaging for additional packaging performance, such gloss, abrasion resistance, thermal resistance, ink protection, and application for near IR detection.
  • polyolefin-based adhesive formulations Inventive Examples 1-5) and traditional polyether/polyester-based adhesive formulations (Comparative Examples A-D) were prepared according to the recipes detailed in Table II and III. The properties of the above formulations are also listed in Tables II and III.
  • Laminates were prepared using oil heated roll hand laminator with the nip temperature set at 65.6 °C (150 °F) at a running speed was set about 0.1 m/s (20 ft/min). Coating weight was adjusted to be from 3.3g/m 2 -3.6g/m 2 (2.0 lbs/ream to 2.2 lbs/ream). The laminates were prepared sheet by sheet about 0.075 m 2 (12 ⁇ 10 in 2 ) coated area. The adhesives were coated using a Meyer rod #3 on the primary film and then completely dried in a 90 °C oven for 3 min to 5 min. The coated primer films were laminated onto the second films by the oil heated hand laminator at about 276 kPa (40 PSI) pressure. The formed laminates were allowed to cure at 45 °C for 2 weeks. The bond strength was tested after 1 day, 7 days and 14 days. Polyolefin films were particularly evaluated, including HDPE/GF-19; BOPE/GF-19; and BOPP/BOPP structures.
  • the T-peel bond strength was measured on a 25 mm (1-inch) strip at a rate of 250 mm/min (10 inches/min) on an Instron tensile tester with a 200 N loading cell. Three strips were tested for each laminate and high and mean strength were recorded together with the failure mode. In case of film tear and film stretch, the high value was reported and in other failure modes the average T-peel bond strength was reported.
  • Typical failure modes include:
  • Laminates were subjected to a boil-in-bag test and the test was conducted as follows: A cured laminate 0.062 m 2 (9 inches ⁇ 11 inches)) was folded over to form a double layer such that the PE film of one layer was in contact with the PE film of the other layer. The edges were then trimmed with a paper cutter to obtain a folded piece about 0.022 m 2 (5 inches ⁇ 7 inches). The edges were then heat sealed to form a pouch with an interior size of 0.015 m 2 (4 inches ⁇ 6 inches). The pouches were then filled 100 mL of 1/1/1 sauce (blend of equal parts by weight of catsup, vinegar and vegetable oil) through the open edge.
  • 1/1/1 sauce blend of equal parts by weight of catsup, vinegar and vegetable oil
  • the pouch was sealed in a manner that minimized the air entrapment inside of the pouch.
  • the filled pouches were then carefully placed in boiling water and kept immersed in the water for 30 min or 60 min. When completed, the extent of tunneling, delamination or leakage was compared with marked preexisting flaws.
  • the bags were then emptied and at least three 1-inch (25 mm) wide strips were cut from the pouches and T-peel bond strength was measured as soon as possible.
  • Laminates were made from the HDPE/GF-19, or BOPE/GF-19 as described above.
  • One of the 23 cm ⁇ 30.5 cm (9 inches ⁇ 12 inches) sheets of laminate was folded over to give a double layer about 23 cm ⁇ 15.3 cm (9 inches ⁇ 6 inches) such that the polymer film of one layer was in contact with the polymer film of the other layer.
  • the edges were trimmed on a paper cutter to give a folded piece about 12.7 cm ⁇ 17.8 cm (5 inches ⁇ 7 inches). Two long sides and one short side was heat sealed at the edges to give a finished pouch with an interior size of 10.2 cm ⁇ 15.2 cm (4 inches ⁇ 6 inches).
  • the heat sealing was done at 177 °C (350 °F) for 1 second at a hydraulic pressure of 276 kPa (40 PSI).
  • Two or three pouches were made for each test.
  • Pouches were filled through the open edge with 25 mL of 1:1:1 sauce (blend of equal parts by weight of ketchup, vinegar and vegetable oil). Splashing the filling onto the heat seal area was avoided as this could cause the heat seal to fail during the test. After filling, the top of the pouch was sealed in a manner that minimized air entrapment inside of the pouch.
  • the seal integrity was inspected on all four sides of pouches to ensure that there were no flaws in the sealing that would cause the pouch to leak during the test. Any defected pouches were discarded and replaced. In some cases, flaws in the laminate were marked to identify whether new additional flaws were generated during the testing.
  • the pouches containing the different sauces at a 1:1:1 ratio were then placed in a convection oven set at 50 °C for 100 hr. The pouches were removed after aging and the extent of tunneling, blistering, de-lamination, or leakage was compared with any of the marked preexisting flaws. The observations were recorded. The pouches were cut open, emptied, and rinsed with soap and water.
  • One or more 2.54 cm (one-inch) strips were cut from the pouches and the laminate bond strength was measured according to the standard bond strength test described earlier. This was done as soon as possible after removing the pouch contents. The interior of the pouches was examined and any other visual defects were recorded.
  • Table IV - Adhesion Performance of Laminate Structure HDPE/Adhesive/LDPE (N/2.54 cm)
  • Example No. Adhesive from Example No. 1 day 7 days 14 days Chemical Aging Boil-in-bag Comp. Ex. F Comp. Ex. A 2.27; AS 3.30; AS 3.34; AS 1.97; AS NM Inv. Ex. 5 Inv. Ex. 1 12.22; AS 12.39; AS/AT 12.13; AS/AT 10.21; AS/FS NM Inv. Ex. 6 Inv.
  • the recyclability was evaluated by remolding the laminated structure of BOPE/Inv. Ex. 3 adhesive/LDPE (Inv. Ex. 3) and comparing the remolded material of Inv. Ex. 3 with a two-layer structure of BOPE/LDPE. The evaluation was conducted by Haake remolding followed by compressing the material to 1 mm thickness sheet.
  • An RS5000 equipped with a Haake Rheomix 3000 mixer with 25 % GF Teflon bushings and cam style rotors were used.
  • the mixer was attached to a RS5000 torque rheometer drive unit and controlled by "System 5", a PC-based control/data acquisition software designed to operate the RS5000 drive.
  • Polymer samples were melt-blended in the heated mixer at a temperature of 160 °C and at a mixing speed of 5 rpm to a maximum of 20 rpm, but the mixing speed was varied to keep mixture below 180 °C for 5 min.
  • a nitrogen purge block was included on top to limit sulfur oxidation. The total mixing time of the mixture was from 20 min to 25 min.
  • Compressed sheet samples were prepared from 15 g to 16 g of the Haake remolded sample in a Carver press at the following conditions: (1) the temperature of the press was 188 °C in a 114 mm ⁇ 114 mm ⁇ 0.89 mm chase; (2) the sample for the first 3 min was in heated platens (platen numbers 1 and 2) of the Carver press; (3) after 3 min, the sample was moved to the lower platens (platen numbers 3 and 4) of the Carver press; and (4) then, the sample was cooled to 20 °C for 3 min. In the above process, bubbles forming on the sheet is not desirable. The resultant sheet is desired to be thinner than 3.18 mm.
  • Table VII describes the results of the measured mechanical properties of laminated structures of BOPE and LDPE with the adhesive of Inventive Example 3 and comparing the properties to a blend of BOPE and LDPE.
  • Table VII - Mechanical Properties of Laminated Structures Example No. Laminate Structure Breaking Stress ⁇ (b) (MPa) Elongation Strain ⁇ (b) (%) Yield Strain ⁇ y (MPa) Elastic Modulus (MPa) Comp. Ex. N BOPE/LDPE -- compressed sheet 25.7 772 11.1 274.8 Inv. Ex. 17 BOPE/Adhesive of Inv. Ex. 3/LDPE - compressed sheet 22.9 695 10.9 269.9

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP20796971.8A 2019-10-28 2020-10-01 Polyolefin-based laminating adhesive composition and recyclable laminate Active EP4051722B1 (en)

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AR120261A1 (es) 2022-02-09
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BR112022007563A2 (pt) 2022-07-05

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